SYNTHESIS OF MULTIFERROIC BiFeO3

MATERIAL BY AUTOCOMBUSTION TECHNIQUE

A THESIS SUBMITTED IN PARTIAL FULFILMENT

OF THE REQUIREMENTS FOR THE DEGREE OF

Bachelor of Technology
In
Ceramic Engineering

By

Binit Kumar Agrawal

Roll – 10508008

Under the Guidance of

Prof. R.Mazumder

Department of Ceramic Engineering

National Institute of Technology ,Rourkela
2005 – 2009
 CERTIFICATE

This is to certify that the thesis entitled “Synthesis of Multiferroic

BiFeO3 Material by autocombustion technique ” submitted by Mr.
Binit Kumar Agrawal in partial fulfilment of the requirements for the
award of Bachelor of Technology Degree in Ceramic Engineering at
National Institute of Technology ,Rourkela (Deemed University) is
an authentic work carried out by him under my supervision and
guidance.

To the best of my knowledge, the matter embodied in

the thesis has not been submitted to any other University / Institute
for the award of any Degree or Diploma.

Date:- Prof. R. Mazumder

Dept. of Ceramic Engg
National Institute of Technology
Rourkela – 769008
 ACKNOWLEDGEMENTS

On the submission of my thesis report of “Synthesis of Multiferroic BiFeO3 Material by

autocombustion technique ”, I would like to convey my gratitude & sincere thanks to my
supervisor Prof R. Mazumder, Department of Ceramic Engineering for his constant
motivation and support during the course of my work in the last one year. I truly
appreciate and value his esteemed guidance and encouragement from the beginning to the
end of this thesis. I am indebted to him for having helped me shape the problem and
providing insights towards the solution.

I want to thank all my teachers and post graduate seniors for providing a solid
background for our studies and research thereafter. They have been great sources of
inspiration to me and I thank them from the bottom of my heart.

Above all, I would like to thank all my friends whose direct and indirect support
helped me completing my project in time. This thesis would have been impossible without
their perpetual moral support.
 Contents

1 General Introduction
1.1 Multiferroic materials
1.2 introduction
1.3 characteristic
1.4 structure
1.5 Doping in BiFeO3
1.6 summary of literature review
1.7 objective of present studies
2 Experimental Work
2.1 autocombustion route
2.2 procedure
2.3 calculations
2.4 choice of fuel
2.5 safety conditions
3. Results and Discussions
3.1 XRD Analysis
4. References
Chapter 1

General Introduction
1.1 Multiferroic Materials
Multiferroic materials, which are a class of materials that yield simultaneous effects of
ferroelectricity, ferromagnetism, and antiferromagnetism in the same material, offer a wide
opportunity for potential applications in information storage, spintronic devices and sensors.
Multiferroic have been formally defined as materials that exhibit more than one primary
ferroic order parameter simultaneously in a single phase. Magnetism and ferroelectricity are
involved with local spins and off-centre structural distortions, respectively. These two seemingly
unrelated phenomena can coexist in certain unusual materials, termed multiferroics.
Multiferroics, sometimes called magnetoelectrics, possess two or more switchable states
such as polarization, magnetization or strain. These compounds present opportunities for
potential applications in information storage, the emerging field of spintronics, and
sensors. Although there are a number of materials that possess both ferroelectricity and
magnetism, it may be surprising that there need not necessarily be a large coupling between
them.
Despite the possible coexistence of ferroelectricity and
magnetism, a pronounced interplay between these properties has rarely been observed . This has
prevented the realization of multiferroic devices offering such functionality. Typical
multiferroics belong to the group of the perovskite transition metal oxides, and include rare-earth
manganites and -ferrites (e.g. TbMnO3, HoMn2O5, LuFe2O4). Other examples are the bismuth
alloys BiFeO3 and BiMnO3, and non-oxides such as BaNiF4 and spinel chalcogenides, e.g.
ZnCr2Se4. These alloys show rich phase diagrams combining different ferroic orders in separate
phases. Apart from single phase multiferroics, composites and heterostructures exhibiting more
than one ferroic order parameter are studied extensively. Some examples include magnetic thin
films on piezoelectric PMN-PT substrates and Metglass/PVDF/Metglass trilayer structures.
Besides scientific interest in their physical properties, multiferroics have potential for
applications as actuators, switches, magnetic field sensors or new types of electronic memory
devices.
Multiferroism and Symmetry

Each multiferroic property is closely linked to symmetry. The primary ferroic properties can be
characterized by their behavior under space and time inversion. Space inversion will reverse the
direction of polarization P while leaving the magnetization M invariant. Time reversal, in turn,
will change the sign of M, while the sign of P remains invariant.

Space Invariant Space Variant

Time Invariant Ferroelastic Ferroelectric

Time Variant Ferromagnetic Ferrotoroidic

Magnetoelectric multiferroics require simultaneous violation of space and time inversion

symmetry. In BiFeO3, off-centering of ions gives rise to an electric polarization, while at a lower
temperature additional magnetic ordering breaks time-reversal symmetry.

In general, a variety of mechanisms can cause lowering of symmetry resulting in multiferroicity

as described below.

Charge Ordered

Mechanism:

A possible origin for a multiferroic state is charge ordering. Such an order can occur in a
compound containing ions of mixed valence and with geometrical or magnetic frustration. These
ions form a polar arrangement, causing improper ferroelectricity (i.e. no ionic displacement). If
magnetic ions are present, a coexisting magnetic order can be established and may be coupled to
ferroelectricity.

Examples: One prominent example for a charge ordered multiferroic is LuFe2O4, which shows
improper ferroelectricity below 330 K. The arrangements of the electrons arise from the charge
frustration on a triangular lattice with the mixed valence state of Fe2+ and Fe3+ ions.
Ferrimagnetic behavior occurs below 240 K.

In addition, charge ordered ferroelectricity is suggested in Fe3O4 and (Pr,Ca)MnO3

Geometrically frustrated multiferroics

Geometric frustrated multiferroicity is related to a structural phase transition at high temperature.

Several compounds belong to this important class of multiferroics: K2SeO4, Cs2CdI4, hexagonal
RMnO3. These systems are proto-typical multiferroics which can be understood by competition
between local interactions on several ion sites. For example, in hexagonal manganites h-RMnO3
(R=Ho-Lu, Y), the ferroelectric polarization at high temperature is correlated to lattice
distortions through off-centering of ions. Geometric frustration gives rise to novel spin
arrangements at low temperature: The spins order in a variety of non-collinear, e.g. (in-plane)
triangular or Kagomé structures in order to relieve the geometric frustration. The coexistence of
ferroelectric and magnetic order occurs together with a strong coupling between two disparate
order parameters.

The mechanism of the ferroelectric ordering in hexagonal RMnO3 is still questionable in

scientific community and must be understood before a comprehensive picture of multiferroic
phenomena in spin frustrated systems can be built. It is still matter of debate whether the
geometric distortion is the origin of the electric polarization or whether the off-centering of Mn
ions also contributes to the polarization.

Physical properties of geometric multiferroics are dominated by the behavior of the d-shell
electrons (eg-orbitals) and of the rare earth elements with an unfilled f-shell. Hexagonal
manganites show the largest deviation from perovskite structure due to the small size of rare-
earth ion. Although geometrically frustrated multiferroics exhibit a simple chemistry, they
provide a unique set of physical properties, such as rich phase diagrams or multiple frustrations.
The strong coupling between ferroelectric and magnetic orders is represented by an anomaly in
the static dielectric constant at magnetic phase transitions. Geometric frustrated ferroelectrics are
prime candidates for device memory applications.

Magnetically driven ferroelectricity

Magnetically driven multiferroics are insulating materials, mostly oxides, in which macroscopic
electric polarization is induced by magnetic long-range order. A necessary but not sufficient
condition for the appearance of spontaneous electric polarization is the absence of inversion
symmetry. In these materials inversion symmetry is broken by magnetic ordering. Such a
symmetry breaking often occurs in so-called frustrated magnets, where competing interactions
between spins favor unconventional magnetic orders. The microscopic mechanisms of
magnetically induced ferroelectricity involve the polarization of electronic orbitals and relative
displacement of ions in response to magnetic ordering.

Many multiferroics show the cycloidal spiral ordering, in which spins rotate around an axis
perpendicular to the propagation vector of the spiral. The induced electric polarization is
orthogonal to the propagation vector and lies in the spiral plane. An abrupt change of the spiral
plane induced by magnetic field results in the corresponding rotation of the polarization vector.
In DyMnO3 this transition is accompanied by the 600% increase of dielectric constant (the giant
magnetocapacitance effect. The microscopic mechanism of magnetoelectric coupling in spiral
multiferroics involves spin-orbit coupling.

E-type Antiferromagnet (I.e. ortho-HoMnO3): In the presence of strong uniaxial anisotropy,

competing interaction can stabilize a *periodic collinear spin arrangement of the up-up-down-
down* type. Such a spin modulation commensurate with the structural or charge modulation can
induce electric polarization via exchange striction mechanism that does not require spin-orbit
coupling.

Lone pair multiferroics

In usual perovskite-based ferroelectrics like BaTiO3, the ferroelectric distortion occurs due to the
displacement of B-site cation (Ti ) with respect to the oxygen octahedral cage. Here the transition
metal ion (Ti in BaTiO3 ) requires an empty “d” shell since the ferroelectric displacement occurs
due to the hopping of electrons between Ti “d” and O p atoms. This normally excludes any net
magnetic moment because magnetism requires partially filled “d” shells. However, partially
filled “d” shell on the B-site reduces the tendency of perovskites to display ferroelectricity.

In order for the coexistence of magnetism and ferroelectricity (multiferroic), one possible
mechanism is lone-pair driven where the A-site drives the displacement and partially filled “d”
shell on the B-site contributes to the magnetism. Examples include BiFeO3, BiMnO3, PbVO3. In
the above materials, the A-site cation (Bi3+, Pb2+) has a stereochemically active 6s2 lone-pair
which causes the Bi 6p (empty) orbital to come closer in energy to the O 2p orbitals. This leads
to hybridization between the Bi 6p and O 2p orbitals and drives the off-centering of the cation
towards the neighboring anion resulting in ferroelectricity.

Applications of Multiferroic Material

Multiferroic composite structures in bulk form are explored for high-sensitivity ac magnetic field
sensors and electrically tunable microwave devices such as filters, oscillators and phase shifters
(in which the ferri-, ferro- or antiferro-magnetic resonance is tuned electrically instead of
magnetically.

In multiferroic thin films, the coupled magnetic and ferroelectric order parameters can be
exploited for developing magnetoelectronic devices. These include novel spintronic devices such
as tunnel magneto resistance (TMR) sensors and spin valves with electric field tunable functions.
A typical TMR device consists of two layers of ferromagnetic materials separated by a thin
tunnel barrier (~2 nm) made of a multiferroic thin film. In such a device, spin transport across
the barrier can be electrically tuned. In another configuration, a multiferroic layer can be used as
the exchange bias pinning layer. If the antiferromagnetic spin orientations in the multiferroic
pinning layer can be electrically tuned, then magnetoresistance of the device can be controlled by
the applied electric field. One can also explore multiple state memory elements, where data are
stored both in the electric and the magnetic polarizations.

Among all the multiferroic materials studied so far, BiFeO3 (BFO)

that exhibits the coexistence of ferroelectric and antiferromagnetic (AFM) orders has received
great attention due to its high ferroelectric Curie point (TC∼1103 K) and the antiferromagnetic
(AFM) Néel point (TN∼647 K) . BFO is one of the prime candidates for room-temperature
magneto electric applications. Multiferroic have potential for applications as actuators, switches,
magnetic field sensors or new types of electronic memory devices.
1.2 Introduction

Bismuth Ferrite (BiFeO3) is an attractive material exhibiting multiferroism at room

temperature, which is ferroelectric (TC = 820–850°C) and anti-ferromagnetic (TN=370–
380°C). BiFeO3 is an inorganic chemical compound with a perovskite structure. It is one of the
most promising lead-free piezoelectric materials by exhibiting multiferroic properties at room
temperature. Multiferroic materials exhibit ferroelectric or anti-ferroelectric properties in
combination with ferromagnetic and antiferromagnetic properties in the same phase. The
multiferroics with a coupling of at least two of the possible three orders (or degrees) of freedom
viz., ferromagnetic (or antiferromagnetic), ferroelectric (or antiferroelectric), and ferroelastic
are rare in nature as transition metal ions with active d electrons tend to reduce the off-center
distortion necessary for ferroelectricity.
BiFeO3 is the most interesting in the family
of a very few single-phase multiferroics because of its high phase transition temperatures (Curie
temp1083K and Neel temperature 675 K). Several techniques have been employed in
synthesizing BiFeO3 In the solid state route Bi2O3 and Fe2O3 are reacted at a temperature in the
range of 800–830 ◦C and unreacted Bi2O3/Bi2Fe4O9 phases are removed by washing in HNO3.
Another technique is simultaneously precipitaton , where a solution of bismuth nitrate and iron
nitrate is treated with ammonium hydroxide to get a hydroxide precipitate. The precipitate needs
calcination at a temperature in the range of 550–750 ◦C to get phase pure BiFeO3. In another
approach nanosized BiFeO3 particles have been prepared by a solution evaporation (tartaric acid
template) technique at a temperature as low as 450 ◦C.
It can also be prepared through co-precipitation (700 ◦C), sonochemical (450 ◦C) and
autocombustion (400 ◦C) routes.Incidentally, there are only a few reports of making densified
and highly resistive BiFeO3 ceramics. Mahesh Kumar et al. [8] reported the dielectric and
ferroelectric properties of BiFeO3 ceramics where BiFeO3 was prepared by solid state route and
there was no report about the bulk densities of the samples. The spontaneous polarization of the
samplewas very low.Wang et al. [9] showed that a rapid liquid-phase sintering of BiFeO3 can
result in 92% of relative density and gave rise to spontaneous and remanent polarization of
8.9,4.0_C/cm2, respectively. Pradhan et al. [10] followed similar rapid phase sintering, but the
percent densification was not reported. In the later case, the spontaneous and remanent
polarizations were only 3.5 and 2.5_C/cm2, respectively instead of earlier reported [9] high
values. Recently, Yuan et al. [11] followed rapid phase sintering technique and synthesized
highly resistive and dense (92% of theoreticaldensity) sample by varying the particle size of
precursors Bi2O3 and Fe2O3 and they reported high spontaneous polarization of their samples.

The various methods which are generally employed for the synthesis of BiFeO3 are
• Solid state reaction Method
• Coprecipitation Method
• Autocombustion Method

1.3 Characteristics
The co-existence of ferroelectricity and ferromagnetism and their coupling with elasticity
provide an extra degree of freedom in the design of new functional sensors and multistate
devices. Due to its multiferroism, an electric field can induce change in magnetization and an
external magnetic field can induce electric polarization. This phenomenon is known as the
magneto electric effect (ME) effect and materials exhibiting this effect are called magneto
electrics or seignetto magnets. Further proof of it being ferromagnetic is that it produces a
hysteresis loop during ferroelectric characterization. The ability to couple to either the electric or
the magnetic polarization allows an additional degree of freedom in device designs.

One of the major drawbacks of BiFeO3 material is the leakage current arising out of its
nonstoichiometry. This is mostly because of the difficulty in obtaining stoichiometric single-
phase BiFeO3 materials. Therefore it allows current to pass through when a high voltage is
applied. Attempts to improve the electrical properties have been made by doping it with rare
earth elements such as lanthanum (La), samarium (Sm), gadolinium (Gd), terbium (Tb) and
dysprosium (Dy) etc. The dopant can be at the A site or the B site. A site being the edges of
the perovskite cell and the B site being the centre of the perovskite cell.
1.4 Structure

BiFeO3 material has got a rhombohedrally

distorted perovskite structure (a = b = c =
5.63 A°, α = β = γ = 59.40) at room
temperature. .A perovskite is any material
with the same type of crystal structure as
calcium titanium oxide (CaTiO3), The
general chemical formula for perovskite
compounds is ABX3, where 'A' and 'B' are
two cations (Bi and Fe) of very different
ionic radii. The 'A' atoms are larger than the
'B' atoms. The ideal cubic-symmetry
structure has the B cation in 6-fold
coordination, surrounded by an
octahedron of anions, and the cation in 12-fold cuboctahedral coordination. The relative ion size
requirements for stability of the cubic structure are quite stringent, so slight buckling and
distortion can produce several lower-symmetry distorted versions, in which the coordination
numbers of A cations, B cations or both are reduced.

(Structure of a perovskite. The chemical formula is of the form "ABX3". The red spheres are X
atoms (usually oxygen), the deep blue spheres are B-site atoms (usually a smaller metal cation,
such as Ti4+), and the green spheres are the A-site atoms (usually a larger metal cation, such as
Ca2+).
1.5 Doping in BiFeO3
In an attempt to get improved properties, there are also a fewreports on doped BiFeO3. Li et al.
[12] reported the crystal structure,electronic structure and magnetic properties of Sr-doped
BiFeO3. Sr-doping increases the oxygen vacancy concentration and Bi1−xSrxFeO3 behaves like
an antiferromagnet and weak ferromagnet simultaneously. Palkar [13] studied the effect of Mn
doping on structural, ferroelectric and magnetic properties of La-modified BiFeO3. Ferroelectric
properties are not affected by Mn substitution but a small enhancement in magnetization is
observed.Jun et al. [14] prepared highly resistive BiFeO3 ceramics by Nb doping and studied
their electric and magnetic properties. They reported a very low remanent polarization of
0.15_C/cm2. Jiang et al. [15] prepared La-doped BiFeO3 by Pechini method followed by
conventional sintering. The dissipation factor reduced to 1%, which is highly desired for
potential applications. However, the reported polarization value was very low and the
microstructure revealed appreciable porosity.
Bi1−xPbxFeO3 ceramics
have been prepared by a simple simultaneous precipitation technique followed by the
conventional sintering process. The sintered density and dielectric property improved with Pb
addition. Typical non-lossy ferroelectric loops (in contrast to lossy loop of BiFeO3) have been
observed in the Bi1−xPbxFeO3 ceramics at room temperature. Pb-doped BiFeO3 powders can be
synthesized by simultaneous precipitation method and their dielectric and ferroelectric properties
are investigated after sintering in air. Bulk densities up to 93% of theoretical density can be
achieved with Pb-doping. The dielectric and ferroelectric properties also improves.

.
Fig. 1. X-ray diffraction patterns of (a) BiFeO3, (b) Bi0.97Pb0.03FeO3, (c)
Bi0.95Pb0.05FeO3, and (d) Bi0.93Pb0.07FeO3.

Figure 1 shows the XRD patterns of pure BiFeO3 and Bi1−xPbxFeO3 (x = 0.03, 0.05 and 0.07)
samples. No impurity phase or excess PbO phase was detected up to x = 0.05. For x = 0.05, small
amounts of Bi2 Fe4O9 and Bi2O3 were formed as impurity phases.From DSC study, it is found that
pure BiFeO3 showed a sharp endothermic peak corresponding to antiferromagnetic to
paramagnetic transition at373 ◦C, but with Pb addition there was no sharp transition. The
absence of a sharp peak and a broad transition point out towards local inhomogeneity, probably
in the nanoscale.

(Fig 2)

Fig. 2 shows the variation of bulk densities of the sintered pellets with Pb addition. In the present
study, the maximum in density ( 93.5%) was achieved for x = 0.05. Further addition of Pb (x =
0.07) lowered the bulk density.
Interestingly, with Pb-doping the grain size decreased drastically. Probably, Pb-doping, up to a
certain level, inhibits grain growth and helps in densification . To understand this behavior,we
have to first note that in BiFeO3, small amounts of Fe2+ ions and oxygen vacancies exist .
Incidentally,BiFeO3 shows p-type conductivity , which can be understood by considering the
substitution of a small amount Fe2+ ions in Fe3+ positions (acceptor doping of Fe3+ by Fe2+)
When PbO is added significantly with respect to pure BiFeO3 after Pb-doping.
1.6 Summary of Literature Review
• The synthesis of BiFeO3 can be done using a variety of techniques
• The most simple and cost effective method of synthesis of BiFeO3 is by autocombustion
route where reaction time is less.
• monophasic nanopowders with zero impurity level at lower temperatures can be prepared
by autocombustion route.
• The fuel/oxidant ratio has clearly the most intense influence on the structural and
morphological properties of the powders.Therefore the quantity of fuel will play a crucial
role in the synthesis of powder.
•
1.7 Objective of the Present Study
The main objective is to produce BiFeO3 which must have the following characteristics :
I. Synthesizing phase pure material,
II. Achieving sintered densities above 90% of theoretical density
III. Getting highly resistive BiFeO3 ceramics with low leakage current.
IV. Achieving good piezoelectric and dielectric properties
Chapter 2

Experimental Work
2.1 Autocombustion Route

One of the most widely used and useful method of preparation of BFO is the combustion
synthesis route using a fuel.The fuel used may be glycine ,citric acid or urea.the precursor
material used for the synthesis of BFO by autocombustion route are BiNO3 and FeNO3 solutions
with a certain concentration level. Combustion synthesis is becoming one of the most popular
methods for the preparation of a wide variety of materials, .The main advantage of using this
tchnique is due to the simplicity, the broad applicability range, the self-purifying feature due to
the high temperatures involved, the possibility of obtaining products in the desired size and
shape. This method is rapidly emerging as one of the most-convenient methods for the
preparation of oxide materials. An aqueous solution of a redox system constituted by the nitrate
ions of the metal precursor, acting as oxidizer, and a fuel like urea, glycine, citric acid or many
others is heated up to moderate temperatures and, upon dehydration, the strongly exothermic
redox reaction develops, which is generally self-sustaining and provides the energy for the
formation of the oxide.
Among the various wet chemical processes, the combustion route is
found to be simple and cost effective for the synthesis of homogeneous, very fine, crystalline
nanopowders without the intermediate decomposition and/or calcination steps which other
conventional synthesis routes would require. The process is based on the mixing of reactants that
oxidize easily, such asmetal nitrates,and an organic fuel, acting as a reducing agent. An external
heat supply is needed to initiate the ignition of the mixture leading to a self-sustainment of an
exothermic redox reaction. In this technique, based on the principles of the propellant chemistry,
a thermally induced redox reaction takes place between an oxidant and a fuel. Many types of
combustion synthesis exist which differ mainly in the physical state of the reactants or in the
combustion modality. By combustion-based methods it is possible to produce monophasic
nanopowders with homogeneous microstructure, at lower temperatures or shorter reaction times,
if compared with other conventional methods like solid-state synthesis or nitrate method.
The various advantages of adopting combustion
synthesis as the prime method for the production of BFO are
• self-purifying feature due to the high temperatures involved,
• the possibility of obtaining products in the desired size and shape.
 • simple and cost effective,
• homogeneous, very fine crystalline nanopowders without the intermediate decomposition
and calcination steps which other conventional synthesis routes would require
• monophasic nanopowders at lower temperatures or shorter reaction times

2.2 Procedure
Bismuth ferrite was prepared by a novel combustion method using glycine as the fuel. The
procedure adopted are
• precursor was prepared in aqueous solution from metal nitrates and glycine.Solutions of
0.2 M Bi(NO3)3 and 0.2M Fe(NO3)3 were prepared.As Bi(NO3)3 is insoluble in water,it
was first dissolved in HNO3.
• 50 ml of both the solutions were then properly mixed in a beaker.
• Glycine/nitrate ratio as taken as 0.1.The appropriate amount of glycine was then added
to the above solution and the mixture was stirred until complete dissolution occurred.
• Then, the mixture was heated and evaporated on a hot plate with stirring till it became a
dark viscous resin. Continuous heating leads to the auto-ignition of dried resin with the
evolution of large quantities of gases.
• The brownish color ash obtained after combustion was analyzed for perovskite-type
BiFeO3 phase.
• The whole process was over after 30 min, but the time between the actual ignition and the
end of the reaction was less than 20 s.
• After the combustion is over in chamber,it is further heated for 5-10 minutes to allow
complete combustion of material.
• After cooling,it is taken out of chamber and grinding is done to achieve finer powder.
• After that,powder was calcined at 450 C for 6 hour The crystal structure of the
synthesized powder was characterized
2.3 Calculation:

Calculation of metal nitrate content

From Fe(NO3)3: 50 ml 0.2 M solution of Fe(NO3)3contains-(0.2/20)*3=0.03 mole of NO3

From Bi(NO3)3: 50 ml 0.2 M solution of Bi(NO3)3 contains-(0.2/20)*3=0.03 mole of NO3

From HNO3: 250 ml solution contain- 60 ml HNO3

50 ml solution contain -12 ml HNO3

NO3 from HNO3=(12*0.7*1.41)/63=0.188 mole of NO3

Total NO3content=.03+0.03+0.188=0.248 mole

Since G/N=0.1

So glycine content=0.0248 mole

Amount of glycine=0.0248*75.05=1.8612 gm

So the final composition of precursor is

• Bi(NO3)3=50 ml

• Fe(NO3)3=50 ML

• Glycin=1.8612 gm

Using Citric acid as fuel

Here Metal content/Citrate content=1

Calculation of metal content

From Fe(NO3)3: 50 ml 0.2 M solution of Fe(NO3)3contains-(0.2/20)*1=0.01 mole of Fe

From Bi(NO3)3: 50 ml 0.2 M solution of Bi(NO3)3 contains-(0.2/20)*1=0.01 mole of Bi
Total metal content=0.01+0.01=0.02 mole
Since M/C=1,

So, C=0.02 mole=0.02*210.14=4.2028 gm

2.4 Choice of fuels:
Physicochemical properties of the oxidepowders synthesized by combustion processes mainly
depend on the nature and amount of fuel used. In order to identify the suitable fuel for the
synthesis of BiFeO3, there are various organic fuels such as urea, citric acid, glycine and sucrose
which are available. Among them, glycine is the best fuel and resulted in the formation of pure
and nano-size BiFeO3 powder. As an easy-obtained product, glycine is low-cost compared with
other organic fuels.
.
F/O ratio may have some effect on the morphology of
the powders calcined at 1000 ◦C, without affecting their phase composition, For example, in FE
samples a very low surface area was measured at F/O = 1.2, which increased for F/O = 2 and
decreased slightly again for higher F/O values. Although the interpretation of this trend is still
not clear, it is in agreement with the correspondent trend of the agglomeration degree with F/O,
according to the fact that for higher agglomeration degrees lower surface areas are obtained
Another example of the effect of F/O ratio on the morphology is the large particle size (540 nm)
and non-homogeneous texture observed for CE powders prepared at F/O = 1, which is probably
caused by the BaCO3 precipitation occurred before the gel formation. In general, low F/O ratios
mean low cost and low organics to burn out, although, high F/O values seem more pertaining.
Nevertheless in some cases high F/O ratios may affect the phase composition of the final
powders, as for CO samples, where some phase segregation occurred for F/O = 4. A
possibleThe F/O ratio has an important effect on the formation temperature of perovskite-type
structure as shown in for FE samples: for F/O = 2 almost 100 wt.% perovskite is present after
calcination at 600 ◦C for 5 h, whereas, at higher F/O values,the diffraction peak of the
perovskite-type structure almost disappears and longer calcinations times at the same
temperature or higher temperatures are necessary in order to obtain the perovskite-type structure.
Explanation of this result can be related on one side with the dependence of the phase
segregation with pH described for CO.
2.5 Safety condition
The auto-combustion reaction can be explosive, yielding a high flame which quickly propagates
through the reactant mixture. Therefore, safety becomes more and more important when
many grams of powder have to be prepared by auto-combustion synthesis, as observed by other
authors. Moreover, if the combustion reaction is more explosive, more powder is displaced from
the combustion beaker and the product is thus lost. Even if the combustion reaction takes place
very calmly, without flame production, only 80% of the product can be recovered at low F/O
ratios, because some of the very fluffy powder flies away with the combustion gases. At F/O =
0.8, where the intensity of the process is decreased, a 90% of recovery can be attained.
For these reasons, in this work, special care has been taken in
the identification of the safety conditions.it is described that the combustion intensity decreases
with F/O ratio and changes with the phase composition of the chemical mixture. Another
important point is the material of the combustion beaker. On this respect, by comparing three
combustion reactors made of different materials (sintered alumina,Pyrex glass and stainless steel)
and by fixing all the other parameters, results show that sintered alumina reactor displays the
highest combustion intensity, whereas stainless steel reactor displays the lowest one. This trend
has been associated with the different dispersion capacity of the three materials. In
summary,when this is possible, higher F/O ratios, lower pH values and combustion reactors with
higher heat dispersion capacity are recommended in order to conduct safely the combustion.
Chapter 3

Result and Discussion

3.1 XRD Analysis
Compared with the traditional solid-state sintering process, the pure BiFeO3 was attained at a
much lower temperature (600 C) without formation of other phase impurities. Moreover,
prepared BiFeO3 nanopowders have a better homogeneity and fine grain morphology in this
case. BiFeO3 nanopowders present the same Neel temperature (TN) and ferroelectric Curie
temperature (TC) as those of bulk BiFeO3, which reveals the multiferroic properties of the
BiFeO3 nanoparticles. The BiFeO3 nanoparticles show a weak ferromagnetic order at room
temperature, which should be attributed to the size-confinement effects of the BiFeO3
nanostructures. The heterometallic polynuclear complexes forming in the solution are the key
reason for synthesizing pure BiFeO3 powder.
The fuel/oxidant ratio has clearly the most intense
influence on the structural and morphological properties of the powders.Low fuel/oxidant ratios
are recommended in some cases in order to avoid segregation of the dopant and to obtain
powders with small particle size. Nevertheless, high fuel/oxidant ratios may be considered a
better choice, in order to avoid dangerous flame production and massive powder volatilization.
Low pH and the use of stainless steel beakers are two other recommended conditions
which decrease the explosivity of the combustion reaction .The fuel/oxidant ratio should be
carefully selected in order to avoid precipitation of the most insoluble compounds or
segregation of the dopant. Moreover, high fuel/oxidant ratio increase the formation temperature
of the perovskite-type structure.The crystal structures of the BFO ceramics were determined by
x-ray diffraction XRD, at a scan rate of 4 deg / min. The figure belo w shows the XRD
patterns of powders calcined at 450 ° C .

B
1 8 0 0

1 6 0 0

1 4 0 0

1 2 0 0

1 0 0 0
intensity

8 0 0

6 0 0

4 0 0

2 0 0

0
1 0 2 0 3 0 4 0 5 0 6 0 7 0
2 Q (d e g re e )
References
[1] H. Schmid, Ferroelectrics 162 (1994) 317.
[2] N.A. Hill, J. Phys. Chem. B 104 (2000) 6694.
[3] J. Wang, J.B. Neaton, H. Zheng, V. Nagarajan, S.B. Ogale, B. Liu, D. Viehland,
V. Vaithyanathan, D.G. Schlom, U.V. Waghmare, N.A. Spaldin, K.M. Rabe, M.
Wuttig, R. Ramesh, Science 299 (2003) 1719.
[4] G.D. Achenback,W.J. James, R. Gerson, J. Am. Ceram. Soc. (1967) 437.
[5] S. Shetty, V.R. Palkar, R. Pinto, Pranama J. Phys. 58 (2002) 1027.
[6] S. Ghosh, S. Dasgupta, A. Sen, H.S. Maiti, J. Am. Ceram. Soc. 88 (2005) 1349.
[7] R. Mazumder, S. Ghosh, P. Mondal, D. Bhattacharya, S. Dasgupta, N. Das, A.
Sen, A.K. Tyagi, M. Sivakumar, T. Takami, H. Ikuta, J. Appl. Phys. 100 (2006)
033908.
[8] M. Mahesh Kumar, V.R. Palkar, K. Srinivas, S.V. Suryanarayana, Appl. Phys. Lett.
76 (2000) 2764.
[9] Y.P.Wang, L. Zhou, M.F. Zhang, X.Y. Chen, J.-M. Liu, Z.G. Liu, Appl. Phys. Lett. 84
(2004) 1731.
[10] A.K. Pradhan, Kai Zhang, D. Hunter, J.B. Dadson, G.B. Loiutts, P. Bhattacharya, R.
Katiyar, D.J. Jun Zhang, Sellmyer, J. Appl. Phys. 97 (2005) 093903.
[11] G.L. Yuan, S.W. Or, Y.P.Wang, Z.G. Liu, J.M. Liu, Solid State Commun. 138 (2006)
76.
[12] J. Li, Y. Duan, H. He, D. Song, J. Alloys Compd. 315 (2001) 259.
[13] V.R. Palkar, D.C. Kundaliya, S.K. Malik, J. Appl. Phys. 93 (2003) 4337.
[14] Y.K. Jun, W.T. Moon, C.-M. Chang, H.-S. Kim, H.S. Ryu, J.W. Kim, K.H. Kim, S.-H.
Hong, Solid State Commun. 135 (2005) 133.
[15] Q.-H. Jiang, C.-W. Nan, Z.-J. Shen, J. Am. Ceram. Soc. 89 (2006) 2123.
[16] V.R. Palkar, R. Pinto, Pramana J. Phys. 58 (2002) 1003.
[17] A.S. Poghossian, H.V. Abovian, P.B. Avakian, S.H. Mkrtchian, V.M. Haroutunian,
Sens. Actuators B 4 (1991) 545.
[18] A.J. Moulson, J.M. Herbert, Electroceramics: Materials, Properties&Application